Phosphorylcholine-containing poly(meth)acrylamide-based copolymers

Abstract

The invention is related to a class of hydrophilic poly(meth)acrylamide-based copolymer comprising dangling (i.e., pendant) phosphorylcholine groups and dangling (i.e., pendant) reactive groups or chains each of which comprises one carboxyl group, one thiol group, or one primary or secondary amino group. The hydrophilic copolymers have a relatively high affinity to a base coating of a polyanionic polymer on a medical device or contact lens and are reactive towards azetidinium groups of an azetidinium-containing polymer upon heating. They can find particular use in producing water-soluble highly-branched hydrophilic polymeric material and in producing water gradient contact lenses.

What is claimed is: 
     
       1. A poly(meth)acrylamide-based copolymer comprising:
 first repeating units each of which is a (meth)acrylamide repeating unit of formula (1) 
 
       
         
           
           
               
               
           
         
         in which R 0  is hydrogen or methyl, R n  is hydrogen or a C 1 -C 4  alkyl group, L 1  is a C 2 -C 4  alkylene divalent radical, PC is a monovalent radical of 
       
       
         
           
           
               
               
           
         
         in which t1 is an integer of 1 to 5 and R 1 ″, R 2 ″ and R 3 ″ independently of one another are C 1 -C 4  alkyl or C 1 -C 4  hydroxyalkyl; and 
         second repeating units which are acrylic repeating units each having a reactive pendant group or chain which comprises a carboxyl group, a thiol group or an amino group of —NHR′ in which R′ is hydrogen or a C 1 -C 4  alkyl group, 
         wherein the poly(meth)acrylamide-based copolymer comprises at least 50% by mole of all (meth)acrylamide repeating units relative to all repeating units of the poly(meth)acrylamide-based copolymer. 
       
     
     
       2. The poly(meth)acrylamide-based copolymer of  claim 1 , wherein the poly(meth)acrylamide-based copolymer comprises at least about 50% by mole of the first repeating units relative to all repeating units of the poly(meth)acrylamide-based copolymer. 
     
     
       3. The poly(meth)acrylamide-based copolymer of  claim 2 , wherein the poly(meth)acrylamide-based copolymer comprises from about 0.01% to about 40% by mole by mole of the second repeating units relative to all repeating units of the poly(meth)acrylamide-based copolymer. 
     
     
       4. The poly(meth)acrylamide-based copolymer of  claim 3 , wherein the second repeating units comprises (meth)acrylate repeating units each of which is a repeating unit of any one of formula (2) to (11) 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         in which R 0  is hydrogen or methyl, X 0  and X 1  independent of each other are —O— or —NR n — in which R n  is hydrogen or a C 1 -C 4  alkyl group, L 2  and L 4  independent of each other are a C 2 -C 4  alkylene divalent radical having 0 or 1 hydroxyl group, L 3  is —CH 2 —CHOH—CH 2 —, R′ is hydrogen or a C 1 -C 4  alkyl group, R a  is hydrogen or methyl, and R b  is hydrogen, C 1 -C 3  alkyl, acetyl, or C 2 -C 4  alkanoylamino which optionally has a carboxyl group, t2 is an integer of 2 to 4, t3 and t4 independent of each other are 0 or 1. 
       
     
     
       5. The poly(meth)acrylamide-based copolymer of  claim 4 , wherein, in formula (3) to (10), X 0  is —NR n — in which R n  is hydrogen or a C 1 -C 4  alkyl group. 
     
     
       6. The poly(meth)acrylamide-based copolymer of  claim 5 , wherein the poly(meth)acrylamide-based copolymer further comprises third repeating units which are acrylic repeating units of one or more acrylic monomers which are free of any carboxyl group or any primary or secondary amino group. 
     
     
       7. The poly(meth)acrylamide-based copolymer of  claim 6 , wherein the third repeating units are selected from the group consisting of 2-(meth)acryloyloxy)ethyl-2′-(trimethylammonio)ethylphosphate, 3-((meth)acryloyloxy)propyl-2′-(trimethylammonio)ethylphosphate, 4-((meth)acryloyloxy)butyl-2′-(trimethylammonio)ethylphosphate, 5-((meth)acryloyloxy)pentyl-2′-(trimethylammonio)ethyl phosphate, 6-((meth)acryloyloxy)hexyl-2′-(trimethylammonio)-ethylphosphate, 2-((meth)acryloyloxy)ethyl-2′-(triethylammonio)ethylphosphate, 2-((meth)acryloyloxy)ethyl-2′-(tripropylammonio)ethylphosphate, 2-((meth)acryloyloxy)ethyl-2′-(tributylammonio)ethyl phosphate, 2-((meth)acryloyloxy)propyl-2′-(trimethylammonio)-ethylphosphate, 2-((meth)acryloyloxy)butyl-2′-(trimethylammonio)ethylphosphate, 2-((meth)acryloyloxy)pentyl-2′-(trimethylammonio)ethylphosphate, 2-((meth)acryloyloxy)hexyl-2′-(trimethylammonio)ethyl phosphate, (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-2-hydroxyethyl (meth)acrylamide, N-3-hydroxypropyl (meth)acrylamide, N-2-hydroxypropyl (meth)acrylamide, N-4-hydroxybutyl (meth)acrylamide, N-5-hydroxypentyl (meth)acrylamide, N-6-hydroxyhexyl (meth)acrylamide, N-(2,3-dihydroxypropyl) (meth)acrylamide, N,N-bis(2-hydroxyethyl) (meth)acrylamide, N-tris(hydroxymethyl)methyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, 2-hydroxyethyl (meth)acrylate, glycerol (meth)acrylate, hydroxypropyl (meth)acrylate, C 1 -C 4 -alkoxy polyethylene glycol (meth)acrylate having a weight average molecular weight of up to 1500 Daltons, N,N-dimethylaminoethyl (meth)acrylate, N-vinylpyrrolidone (NVP), N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide, N-vinyl-N-methyl acetamide, N-methyl-3-methylene-2-pyrrolidone, 1-ethyl-3-methylene-2-pyrrolidone, 1-methyl-5-methylene-2-pyrrolidone, 1-ethyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone, 5-ethyl-3-methylene-2-pyrrolidone, allyl alcohol, vinyl alcohol, and combinations thereof. 
     
     
       8. A water-soluble thermally-crosslinkable polymeric material, comprising:
 (a) one or more first polymer chain of an azetidinium-containing polymer having azetidinium groups; 
 (b) one or more second polymer chains of a poly(meth)acrylamide-based copolymer of  claim 1 , wherein each second polymer chain is covalently attached to one of said one or more first polymer chains via at least one linkage formed between one azetidinium group of the azetidinium-containing polymer and one reactive pendant group or chain of the poly(meth)acrylamide-based copolymer; and 
 (c) azetidinium groups each of which is embedded in or covalently attached to one of said one or more first polymer chains. 
 
     
     
       9. The water-soluble thermally-crossklinkable polymeric material of  claim 8 , wherein the azetidinium-containing polymer is polyamidoamine-epichlorohydrin (PAE). 
     
     
       10. The water-soluble thermally-crosslinkable polymeric material of  claim 8 , wherein the azetidinium-containing polymer is a poly(2-oxazoline-co-ethyleneimine)-epichlorohydrin. 
     
     
       11. The water-soluble thermally-crosslinkable polymeric material of  claim 8 , wherein the azetidinium-containing polymer is a homopolymer of an azetidinium-containing vinylic monomer. 
     
     
       12. The water-soluble thermally-crosslinkable polymeric material of  claim 8 , wherein the azetidinium-containing polymer is a copolymer of an azetidinium-containing vinylic monomer with one or more hydrophilic vinylic monomers. 
     
     
       13. The water-soluble thermally-crosslinkable polymeric material of  claim 8 , wherein the water-soluble thermally-crosslinkable polymeric material comprises (i) from about 20% to about 95% by weight of the first polymer chains and (ii) from about 5% to about 80% by weight of the second polymer chains. 
     
     
       14. A packaging solution, which is an aqueous solution comprising at least one buffering agent for maintaining a pH of from about 6.0 to about 8.5 and from about 0.01% to about 2% by weight of a water-soluble and thermally-crosslinkable hydrophilic polymeric material of  claim 8 , wherein the packaging solution has a tonicity of from about 200 to about 450 milliosmol (mOsm) and a viscosity of from about 1 centipoise to about 20 centipoises at 25° C. 
     
     
       15. The packaging solution of  claim 14 , wherein the aqueous solution comprises from about 0.05% to about 1.5% by weight of the water-soluble thermally-crosslinkable hydrophilic polymeric material.